Microstructure and magnetic properties of Fe72.5Cu1M2V2Si13.5B9 (M=Nb, Mo, (NbMo), (MoW)) nanocrystalline alloys

The microstructure and magnetic properties of Finemet-type Fe_72.5Cu₁M₂V₂Si_13.5B₉ (M=Nb, Mo, (NbMo), (MoW)) alloys have been systematically studied. Results show that the nanocrystalline alloy with M=NbMo has the smallest grain size of about 8 nm. The order of the effect of Nb, Mo and W additions in decreasing the α-Fe grain size in nanocrystalline alloys is Nb>Mo>W. The best DC soft magnetic properties are obtained in the alloy with M=Nb. In the case of AC soft magnetic properties, the Nb alloy also exhibits a very low core loss comparing with typical Finemet alloy. Therefore, the Nb alloy is suitable for use as a transformer core material. In addition, it is shown that a narrow grain size distribution and a uniform dispersion of α-Fe grains in the amorphous matrix are very crucial for the development of new Finemet-type nanocrystalline alloys with good soft magnetic properties.     

Grain growth process of two-phase nanocrystalline soft magnetic materials

In order to clarify the origin of the high thermal stability of the microstructure in bcc-Fe/amorphous two-phase nanocrystalline soft magnetic materials, we have investigated the changes in the magnetic and microstructural properties upon isothermal annealing at 898 K for an Fe₈₉Zr₇B₃Cu₁ alloy by means of transmission electron microscopy, Mössbauer spectroscopy and DC magnetometry. The mean grain size was found to remain almost unchanged at the early stage of annealing. However, rapid grain coarsening was evident at an annealing time of 7.2 ks where the intergranular amorphous phase begins to crystallize into Fe₂₃Zr₆. The grain growth process with a kinetic exponent of 1.6 is observed for the growth process beyond this annealing time, reflecting the disappearance of the intergranular amorphous phase. Our results confirm that the thermal stability of the bcc-Fe/amorphous two-phase nanocrystalline soft magnetic alloys is governed by the residual amorphous phase.     

Phase segregation in the Fe90Zr10 amorphous alloy under heating

A study of the changes in the structure of melt-quenched Fe₉₀Zr₁₀ amorphous alloys by x-ray diffraction, Auger spectroscopy, and transmission electron microscopy is reported. The samples were subjected to isochronous (for 1 h) and isothermal anneals at 100–650 °C. It is shown that an amorphous alloy annealed for one hour at 300–500 °C crystallizes with formation of a supersaturated solid solution of Zr in α Fe and the intermetallic compound Fe₃Zr. Isothermal anneal at 100 °C for up to 7000 h produces nanocrystallites 110–30 nm in size, with fuzzy interfaces between the grains. An alloy subjected to such an anneal contains two solid solutions of Zr in Fe, having a cubic and a weakly tetragonal lattice. Crystallization taking place during low-temperature anneals is preceded by phase segregation of the alloy within the amorphous state. The lattice periods of the solid solutions have been determined. The possibility of the alloy crystallizing by spinodal decomposition during prolonged annealing is discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 1769–1772 (October 1998)     

Formation of boride phases from individual powder components during the mechanical synthesis of Ni<Subscript>80</Subscript>Mo<Subscript>7</Subscript>B<Subscript>13</Subscript> alloy

Ni₈₀Mo₇B₁₃ nanocrystalline alloy containing a Ni(Mo,B) face-centered cubic (FCC) solid solution of the substitutional-interstitial type was obtained by high-energy ball milling of the component mixtures. In the temperature range 400–700°C, the metastable solid solution Ni(Mo,B) decomposes, leading to the formation of metastable FCC Ni(Mo) and HCP MoB₄ phases. Upon isothermal annealing at 1000°C for1 h, the alloy transforms into the stable state and contains the equilibrium phases FCC Ni(Mo), cubic Ni₂₁Mo₂B₆, and orthorhombic Ni₃B.     

Dependence of Magnetic Properties on Composition of Nanocrystalline Fe–M–B–Cu (M: Zr,Nb, Mo,Ti, Ta) Alloys

The specialized rf-Mössbauer technique is used to elucidate the magnetic properties of NANOPERM-type nanocrystalline alloys. The influence of alloy composition on the soft magnetic properties is studied for the Fe₈₀M₇B₁₂Cu₁ (M: Ti, Ta, Nb, Mo, Zr) alloys. The rf-Mössbauer experiments allowed us to distinguish magnetically soft nanoclusters from magnetically harder microcrystalline phases. The measurements performed as a function of the rf field intensity allowed the determination of the distribution of anisotropy fields related to the size distribution of bcc nanoclusters. Smaller anisotropy fields in the nanocrystalline phase were found in Nb-, Zr-, and Mo-containing alloys as compared with the alloys which contain Ti and Ta. The Mössbauer measurements were supplemented by X-ray diffraction determination of the size of nanocrystalline grains.     

退火温度对硼掺杂纳米金刚石薄膜微结构和p型导电性能的影响

采用热丝化学气相沉积法制备硼掺杂纳米金刚石 (BDND) 薄膜, 并对薄膜进行真空退火处理, 系统研究退火温度对BDND薄膜微结构和电学性能的影响. Hall效应测试结果表明掺B浓度为5000 ppm (NHB) 的样品的电阻率较掺B浓度为500 ppm (NLB) 的样品的低, 载流子浓度高, Hall迁移率下降. 1000 ℃退火后, NLB和NHB 样品的迁移率分别为53.3和39.3 cm²·V^-1·s^-1, 薄膜的迁移率较未退火样品提高, 电阻率降低. 高分辨透射电镜、紫外和可见光拉曼光谱测试结果表明, NLB样品的金刚石相含量较NHB样品高, 高的硼掺杂浓度使薄膜中的金刚石晶粒产生较大的晶格畸变. 经1000 ℃退火后, NLB和NHB薄膜中纳米金刚石相含量较未退火时增大, 说明薄膜中部分非晶碳转变为金刚石相, 为晶界上B扩散到纳米金刚石晶粒中提供了机会, 使得纳米金刚石晶粒中B浓度提高, 增强纳米金刚石晶粒的导电能力, 提高薄膜电学性能. 1000 ℃退火能够恢复纳米金刚石晶粒的晶格完整性, 减小由掺杂引起的内应力, 从而提高薄膜的电学性能. 可见光Raman光谱测试结果表明, 1000℃退火后, Raman谱图中反式聚乙炔 (TPA) 的1140 cm^-1峰消失, 此时薄膜电学性能较好, 说明TPA减少有利于提高薄膜的电学性能. 退火后金刚石相含量的增大、金刚石晶粒的完整性提高及TPA含量的大量减少有利于提高薄膜的电学性能. 关键词： 硼掺杂纳米金刚石薄膜 退火 微结构 电学性能     

磷离子注入纳米金刚石薄膜的n型导电性能与微结构研究

系统研究了磷离子注入并在不同温度退火后的纳米金刚石薄膜的微结构和电学性能.研究表明,当退火温度达到800 ℃以上时,薄膜呈良好的n型电导.Raman光谱和电子顺磁共振谱的结果表明,薄膜中金刚石相含量越高和完整性越好,薄膜电阻率越低. 这说明纳米金刚石晶粒为薄膜提供了电导.1000 ℃退火后,薄膜晶界中的非晶石墨相有序度提高,碳悬键数量降低,薄膜电阻率升高.薄膜导电机理为磷离子注入的纳米金刚石晶粒提供了n型电导,非晶碳晶界为其电导提供了传输路径. 关键词： 纳米金刚石薄膜 n型 磷离子注入     

Influence of composition on hyperfine interactions in FeMoCuB nanocrystalline alloy

Influence of varying Fe/B ratio upon hyperfine interactions is investigated in the Fe_91?x Mo₈Cu₁B_x rapidly quenched alloys. They are studied both in the as-quenched (amorphous) state as well as after one-hour annealing at different temperatures ranging from 330 °C up to 650 °C. Such a heat treatment causes significant structural changes featuring a formation of nanocrystalline bcc-Fe grains during the first crystallization step. At higher annealing temperatures, a grain growth of bcc-Fe and occurrence of additional crystalline phases are observed. The relative fraction of the crystalline phase governs the development of magnetic hyperfine fields in the residual amorphous matrix even if this was fully paramagnetic in the as-quenched state. The development of hyperfine interactions is discussed as a function of annealing temperature and composition of the investigated alloys. ⁵⁷Fe Mössbauer spectrometry was used as a principal analytical method. Additional information related to the structural arrangement is obtained from X-ray diffractometry. It is shown that in the as-quenched state, the relative fraction of magnetic hyperfine interactions increases as the amount of B rises. In partially crystalline samples, the contribution of magnetic hyperfine interactions inside the retained amorphous matrix increases with annealing temperature even though the relative fraction of amorphous magnetic regions decreases.     

Disclination Mechanism of Plastic Deformation of Nanocrystalline Materials

A model describing mechanical behaviour of nanocrystalline materials (NC) obtained by crystallization from amorphous precursor is presented. In the framework of this model a structure of such NCs is represented as a composite consisting of amorphous matrix and absolutely rigid inclusions corresponding to crystalline phase. Dependencies of stress concentration coefficient and yield stress of NCs on the average grain size are obtained. It is shown that the dependence of the yield stress has a point of inflection at the critical grain size in the range of 20–25 nm and is inverse to the Hall-Petch relationship at grain sizes smaller than the critical one. The model predicts a formation of a superlattice from disclinations located in triple junctions of grains on the stage of NC plastic flow. A process of the plastic flow of NC's amorphous matrix and amorphous metallic alloys is described as a go-ahead mechanism of dislocation movement, which includes emission, absorption and reemission of dislocations by disclinations.     

Nanostructures, disordered ferromagnetism and spin glasses

Magnetic systems with a considerable amount of irregular interfaces were investigated by ⁵⁷Fe Mössbauer spectroscopy. Chemically homogeneous ferromagnets around the percolation threshold composition of disappearing magnetism and chemically heterogeneous alloys prepared by nanocrystallization of amorphous alloys belong to this class of materials. Low temperature and high field measurements were performed on nanocrystalline FeZrBCu alloys, on ball‐milled Fe with nano‐size grains and on melt‐quenched amorphous Fe–Zr and Fe–Y alloys in order to clarify the origin of large high‐field susceptibility and to investigate the common features of the approach to magnetic saturation. Curie point determination of the residual amorphous phase in the nanocrystalline FeZrBCu alloys, results on the structure of the nanocrystalline b.c.c. phase and of the interfacial region will be reported.     

Structural changes during annealing of submicro- and nanocrystalline aluminum alloys

The annealing-induced evolution of the structure and microhardness of submicro-and nanocrystalline Al—3% Mg and Al 1570 alloys produced by torsional severe plastic deformation are studied. Annealing of the Al-3% Mg alloy at 373–423 K and annealing of the Al 1570 alloy at 373–473 K are shown to result in the relaxation of internal stresses and subsequent normal grain growth. As the annealing temperature increases, the microhardness decreases. At higher temperatures (473 K for the Al—3% Mg alloy and 573 K for the Al 1570 alloy), anomalous grain growth takes place. This growth is accompanied by the appearance of numerous grains with a high dislocation density, a high concentration of impurity atoms in grain boundaries, and an increase in the microhardness. These effects are explained.     

Microstructure and mechanical properties of a large-dimensional bulk nanocrystalline-based Fe–Al–Cr alloy prepared by an aluminothermic reaction casting and followed annealing at 1000 °C

A large-dimensional bulk nanocrystalline phase-based Fe–Al–Cr alloy with 10?wt.% Cr, which was about 200?mm in diameter and 10?mm in thickness, was prepared by an aluminothermic reaction casting and followed annealing at 1000?°C. Microstructures of the alloy were investigated by optical microscope, electron probe microscope, scanning electron microscope attached with electron backscattered diffraction, X-ray diffraction and transmission electron microscope. The magnetization curves of the alloy were tested by Lake Shore 7410 vibrating sample magnetometer. Compressive properties of the alloy were tested. The results show the alloy was consisted of a Fe–Al–Cr nanocrystalline matrix, Cr₇C₃ phase and contaminants in micrometre. Average grain size of the nanocrystalline matrix was 19?nm. Volume fraction of the Cr₇C₃ phase in the alloy was about 4.5%. After annealing, the saturated intensity of magnetization and the specific magnetic susceptibility of the alloy increased slightly from 99 emu/g and 0.083 emu/g?Oe to 104 emu/g and 0.113 emu/g?Oe, respectively. Compressive strength of the alloy was 1200?MPa and much higher than that of the small-scale nanocrystalline alloy and alloy with grains in micrometre.     

Formation and structure of nanocrystals in an Al86Ni11Yb3 alloy

The formation and structure of the nanocrystalline phase in the Al₈₆Ni₁₁Yb₃ alloy are investigated using differential scanning calorimetry (DSC), transmission electron and high-resolution electron microscopy, and x-ray diffraction. The nanocrystalline phase is formed upon controlled crystallization of the amorphous alloy prepared by quenching of the melt on a rapidly moving substrate. It is revealed that the nanocrystalline alloy consists of aluminum nanocrystals (5–12 nm in size) randomly distributed in the amorphous matrix. The maximum fraction of the nanocrystalline phase does not exceed 25%. The nanocrystal size substantially increases at the initial stage of isothermal treatment (at 473 K) and then changes insignificantly. It is found that nanocrystals are usually free of defects. However, some nanocrystals have a more complex microstructure with twins and dislocations. The size distributions of nanocrystals are determined at several durations of isothermal treatment. It is demonstrated that the nucleation of nanocrystals predominantly occurs through the heterogeneous mechanism. The experimental distributions are compared with those obtained from a computer simulation. The activation energy of crystallization, the time-lag, and the coefficient of ytterbium diffusion in the alloy are estimated     

Nanoscale combined reactions: non-equilibrium α-Co formation in nanocrystalline ϶-Co by abnormal grain growth

Electrodeposited nanocrystalline Co offers a relatively unique opportunity to study the interaction of two fundamentally different elementary solid state reactions: grain growth and ε (HCP) to α (FCC) allotropic phase transformation. Samples were isothermally annealed at temperatures above and below the equilibrium transformation temperature (T_εα?=?695?K) and quenched to ambient for subsequent characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Isothermal annealing above 695?K resulted in concurrent grain growth and ε to α transformation. Unexpectedly, however, simultaneous grain growth and ε to α transformation also occurred during isothermal annealing at temperatures as low as 573?K, i.e. 122?K below the expected equilibrium T_εα. It was observed that non-equilibrium α-Co formed within a matrix of nanocrystalline ε-Co via abnormal grain growth, and is therefore fundamentally different from the ε to α transformation typically observed in conventional polycrystalline Co.     

Ni-WC composite coatings by carburizing electrodeposited amorphous and nanocrystalline Ni-W alloys

In situ formation of tungsten carbide in the matrix of FCC nickel has been achieved by carburizing of the electrodeposited Ni-W alloy coatings. The size of the carbide particles ranges between 100 and 500 nm. The carbide phase is also present in the form of very small precipitates inside the nickel grains. The size of such precipitates is between 10 and 40 nm. The carburizing environment was created by introducing a flowing mixture of vaporized 95.5% alcohol (0.25 ml/min, liquid) and argon (0.5 L/min, gas) into the carburizing furnace. Supersaturated nature of electrodeposited amorphous and nanocrystalline alloys, in addition to high diffusivity, have been attributed for the formation of carbide phase in the deposits at a temperature range of 700-850 °C. The carbide-metal interface is clean and the composite coatings are compact. Hardness values up to about 1100 KHN are achieved. Hardness increases with tungsten content and carburizing temperature.     

A study on anomalous yield drop behaviour in modified beta titanium alloys

ABSTRACT

The yield drop phenomenon observed in the Ti–15V-3Al–3Sn-3Cr (Ti–15–3) beta-titanium alloy and its anomalous behaviour in the boron and carbon added Ti–15–3 alloys have been studied. While the base and the carbon containing alloys exhibit yield drop, the boron containing alloy with smaller grain size than base alloy does not appear to show this phenomenon. Tensile tests were interrupted at different stress levels followed by analyses of slip lines and sub-structural characteristics using scanning and transmission electron microscopes to understand this anomalous yield point phenomenon. Infrared thermal imaging technique was used to map the strain localisation and the spatiotemporal evolution of deformation along the gauge length of the specimens during the tensile tests. Deformation in these alloys initiates only in a few grains. Pile-up of dislocations in these grains subsequently triggers the formation of dislocations in other grains and their rapid multiplications. The spreading of deformation by the generation of dislocations from pile up dislocations in one grain to neighbouring un-deformed grains and their rapid multiplication to new regions influence the yield drop phenomenon and its characteristics. It is shown in this study that microscopic instability in the grain level is a necessary, but not the sufficient condition for the manifestation of macroscopic instability during tensile deformation in polycrystalline materials. The presence of boride particles at grain boundaries restricts the slip transfer across the grains as well as the spreading of deformation to new regions, which causes the suppression of yield drop in the boron containing alloy.     

Nanocrystalline iron-based alloys investigated by Mössbauer spectrometry

Nanocrystalline alloys exhibit great fundamental and technological interests because of their microstructural properties, and their excellent soft magnetic properties. ⁵⁷Fe Mössbauer spectrometry is a well suitable technique to investigate Fe-based nanocrystalline alloys: its local probe behaviour permits to elucidate the nature of hyperfine interactions at different resonating iron nuclei and to distinguish their immediate atomic surroundings. We review on the recent Mössbauer developments performed on first FeCuMBSi and then FeCuBSi nanocrystalline alloys. From Mössbauer studies, one can estimate the crystalline (i.e., amorphous) fraction, the Si-content in Fe--Si nanocrystalline grains emerging from amorphous alloys of the first series, the temperature dependence of magnetic behaviours of both crystalline and amorphous phases; finally, we present a novel fitting procedure applied to FeCuBSi nanocrystalline alloys which result from bcc-Fe crystalline grains embedded in an amorphous matrix. In this case, the hyperfine structure is able to model the intergranular phase.     

Photoemission and electronic structure of Mo,Ru and Amorphous MoRuB and MoRuP

The electronic structures of molybdenum, ruthenium and amorphous Mo₄₈ Ru₃₂ B₂₀ and Mo₄₀ Ru₄₀ P₂₀ are investigated by the XPS and UPS techniques. The experimental results of pure elements are in agreement with previous band calculations. The valence bands of the amorphous alloys are quite comparable to those obtained from pure Mo and Ru assuming hypothetical alloys. For the investigated alloys, the electronic DOS's at the Fermi level are intermediate between those of transition metal components. The disordering on the band structure, due to alloying effects, is found to be larger for the phosphorus based alloy than for the boron one. A qualitative band model can explain the various observed properties; the experimental results are also discussed in relation with the atomic volumes.     

NANOSTRUCTURED Zr-BASED ALLOYS-PHASE FORMATION AND MECHANICAL PROPERTIES

Newly developed nanostructured Zr/Ti-Al-TM multiphase alloys can provide a large bandwidth of interesting properties, such as mechanical properties. Bulk materials with nanocrystalline/ amorphous and (nano)quasicrystalline/ amorphous microstructure with different volume fractions of nanophases and with different grain sizes can be obtained by slowly cooling the melt as well as by solid state reactions. Multiphase structures are realized either by partial de-vitrification of bulk glass-forming alloys or by defined addition of inert compounds upon alloying. Special preparation techniques e.g. copper mould casting and subsequent controlled annealing and mechanical alloying combined with hot consolidation of powders are described. The phase formation and transformation processes and the thermal stability of such materials in dependence on alloy composition and processing parameters are discussed in detail. Currently, the exploration of properties with respect to potential applications of these nanostructured alloys is still at the beginning. First investigations on the contributions of different phases/ volume fractions to the overall mechanical behaviour will be shown. At room temperature, the deformation behaviour of amorphous/crystalline bulk samples is governed by contributions of all existing phases yielding a high strength of the material.     

Temperature dependence of the Mössbauer spectra of amorphous and nanocrystallized Fe86Zr7Cu1B6

Mössbauer measurements have been performed on amorphous and nanocrystalline alloy ribbons of nominal composition Fe₈₆Zr₇Cu₁B₆. The nanocrystalline samples were obtained by annealing the as-quenched alloy at different temperatures in the range between 650 and 870 K. Mössbauer spectra of the as-quenched amorphous sample have been recorded at 77 K, room temperature and above the Curie temperature (330 K) at 360 K. We have also performed Mössbauer measurements at room temperature in the nanocrystalline alloys to characterize the phases that appear after the annealing and their relative concentration. The as-quenched sample spectra reveal the existence of two inequivalent sites for Fe. Such a feature is also observed in the remaining amorphous phase of the annealed samples. In the first steps of crystallization, -Fe precipitates and its concentration increases with the annealing temperature. The experimental results suggest that the composition of the whole amorphous phase does not suffer large changes during crystallization.